Remediation options to reduce bioaccessible and bioavailable lead and arsenic at a smelter impacted site - consideration of treatment efficacy.

In this study, smelter contaminated soil was treated with various soil amendments (ferric sulfate [Fe2(SO4)3], triple superphosphate [TSP] and biochar) to determine their efficacy in immobilizing soil lead (Pb) and arsenic (As). In soils incubated with ferric sulfate (0.6M), gastric phase Pb bioaccessibility was reduced from 1939 ± 17 mg kg-1 to 245 ± 4.7 mg kg-1, while intestinal phase bioaccessibility was reduced from 194 ± 25 mg kg-1 to 11.9 ± 3.5 mg kg-1, driven by the formation of plumbojarosite. In TSP treated soils, there were minor reductions in gastric phase Pb bioaccessibility (to 1631 ± 14 mg kg-1) at the highest TSP concentration (6000 mg kg-1) although greater reductions were observed in the intestinal phase, with bioaccessibility reduced to 9.3 ± 2.2 mg kg-1. Speciation analysis showed that this was primarily driven by the formation of chloropyromorphite in the intestinal phase following Pb and phosphate solubilization in the low pH gastric fluid. At the highest concentration (10% w/w), biochar treated soils showed negligible decreases in Pb bioaccessibility in both gastric and intestinal phases. Validation of bioaccessibility outcomes using an in vivo mouse assay led to similar results, with treatment effect ratios (TER) of 0.20 ± 0.01, 0.76 ± 0.11 and 1.03 ± 0.10 for ferric sulfate (0.6M), TSP (6000 mg kg-1) and biochar (10% w/w) treatments. Results of in vitro and in vivo assays showed that only ferric sulfate treatments were able to significantly reduce As bioaccessibility and bioavailability with TER at the highest application of 0.06 ± 0.00 and 0.14 ± 0.04 respectively. This study highlights the potential application of ferric sulfate treatment for the immobilization of Pb and As in co-contaminated soils.

Impact of smelter re-development on spatial and temporal airborne Pb concentrations.

Total suspended particulate (TSP) and PM10 filters collected from two ambient air monitoring stations in Port Pirie were analysed to determine the impact of a lead (Pb) smelter redevelopment on air quality parameters including total elemental concentration, Pb isotopic ratio, Pb bioaccessibility and Pb speciation. Filters from 2009 to 2020 were analysed with a focus on samples from 2017 (immediately prior to smelter redevelopment) and 2020 (post-smelter redevelopment). Lead concentration in 2009-2020 TSP was variable ranging up to 6.94 µg m-3 (mean = 0.57 µg m-3), however, no significant decrease in Pb concentration was observed at either Port Pirie West (p = 0.56, n = 34) or Oliver Street (p = 0.32, n = 28) monitoring stations when 2017 and 2020 TSP values were compared. Similarly, no significant difference (p = 0.42) in PM10 Pb concentration was observed in 2017 (mean = 0.80 µg m-3) and 2020 (0.60 µg m-3) Oliver Street filters. Although no change in percentage Pb bioaccessibility was observed when 2017 and 2020 Port Pirie West TSP samples were compared (mean of 88.7% versus 88.0%), Pb bioaccessibility was lower (p < 0.005) in both 2020 TSP (mean of 83.9% versus 62.9%) and PM10 (mean of 70.8% versus 58.3%) Oliver Street filters compared to 2017. While scanning electron microscopy, energy dispersive x-ray spectroscopy identified a number of Pb phases within filters (galena, anglesite, cerussite, conglomerates), differences in Pb speciation between 2017 and 2020 filters could not be identified although it was presumed that this influenced Pb bioaccessibility outcomes at Oliver Street. Data from this study suggests that recent smelter redevelopments have not significantly decreased the concentrations of airborne Pb in Port Pirie although re-entrainment of soil-Pb from historical impact may also be a contributing Pb source.

Assessment of soil metal concentrations in residential and community vegetable gardens in Melbourne, Australia.

Gardening and urban food production is an increasingly popular activity, which can improve physical and mental health and provide low cost nutritious food. However, the legacy of contamination from industrial and diffuse sources may have rendered surface soils in some urban gardens to have metals value in excess of recommended guidelines for agricultural production. The objective of this study was to establish the presence and spatial extent of soil metal contamination in Melbourne's residential and inner city community gardens. A secondary objective was to assess whether soil lead (Pb) concentrations in residential vegetable gardens were associated with the age of the home or the presence or absence of paint. The results indicate that most samples in residential and community gardens were generally below the Australian residential guidelines for all tested metals except Pb. Mean soil Pb concentrations exceeded the Australian HIL-A residential guideline of 300 mg/kg in 8% of 13 community garden beds and 21% of the 136 residential vegetable gardens assessed. Mean and median soil Pb concentrations for residential vegetable gardens was 204 mg/kg and 104 mg/kg (range <4-3341 mg/kg), respectively. Mean and median soil Pb concentration for community vegetable garden beds was 102 mg/kg and 38 mg/kg (range = 17-578 mg/kg), respectively. Soil Pb concentrations were higher in homes with painted exteriors (p = 0.004); generally increased with age of the home (p = 0.000); and were higher beneath the household dripline than in vegetable garden beds (p = 0.040). In certain circumstances, the data indicates that elevated soil Pb concentrations could present a potential health hazard in a portion of inner-city residential vegetable gardens in Melbourne.